WO2002016296A1 - Catalyseur ameliore de la decomposition de l'hydroperoxyde - Google Patents

Catalyseur ameliore de la decomposition de l'hydroperoxyde Download PDF

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Publication number
WO2002016296A1
WO2002016296A1 PCT/US2000/022867 US0022867W WO0216296A1 WO 2002016296 A1 WO2002016296 A1 WO 2002016296A1 US 0022867 W US0022867 W US 0022867W WO 0216296 A1 WO0216296 A1 WO 0216296A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
catalyst
gold
chhp
hydroperoxide
Prior art date
Application number
PCT/US2000/022867
Other languages
English (en)
Inventor
Norman Herron
Stephan Schwarz
Joe Douglas Druliner
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to CNB008198322A priority Critical patent/CN1203041C/zh
Priority to AU2000267916A priority patent/AU2000267916A1/en
Priority to US10/344,443 priority patent/US6806390B1/en
Priority to EP00955769A priority patent/EP1309534B1/fr
Priority to DE60023358T priority patent/DE60023358T2/de
Priority to KR10-2003-7002297A priority patent/KR20030034145A/ko
Priority to JP2002521172A priority patent/JP2004506703A/ja
Priority to PCT/US2000/022867 priority patent/WO2002016296A1/fr
Publication of WO2002016296A1 publication Critical patent/WO2002016296A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
    • B01J31/124—Silicones or siloxanes or comprising such units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention generally relates to an improved catalytic process for decomposing alkyl or aromatic hydroperoxides to form a mixture containing the corresponding alcohol and ketone.
  • the invention relates to decomposing a hydroperoxide by contacting it with a catalytic amount of a heterogeneous Au catalyst that has been treated with an organosilicon reagent.
  • cyclohexane is oxidized to form a reaction mixture containing cyclohexyl hydroperoxide (CHHP).
  • CHHP cyclohexyl hydroperoxide
  • the resulting CHHP is either decomposed or hydrogenated, optionally in the presence of a catalyst, to form a reaction mixture containing cyclohexanol and cyclohexanone.
  • K/A ketone/alcohol
  • adipic acid or caprolactam which are important reactants in processes for preparing certain condensation polymers, notably polyamides.
  • a high K/A ratio in the reaction mixture is generally preferred. Due to the large volumes of adipic acid consumed in these and other processes, improvements in processes for producing adipic acid and its precursors can be used to provide beneficial cost advantages.
  • Druliner et al. (WO 98/34894) used a heterogeneous gold catalyst in an improved catalytic process for decomposing alkyl or aromatic hydroperoxides to form a mixture containing the corresponding alcohol and ketone.
  • Organosilicon compounds have for some time been employed in the treatment of inorganic oxide surfaces such as inorganic oxide films, particulates and pigments, and fibers (such as glass fibers, aluminum fibers and steel fibers).
  • the typical organosilicon treatment involves coating such surfaces with a hydrolyzate (and/or condensate of the hydrolyzate) of an organofunctional hydrolyzable silane.
  • the treatment is typically supplied to the surface of the inorganic oxide whereby through the hydrolyzable groups or silanol groups ( ⁇ Si-OH), bonding through siloxy moieties ( ⁇ Si-O-) is effected.
  • U.S. Patent No. 2,722,504 modified the contact efficiency of catalysts and other materials by the incorporation of alkyl silanes onto the surface.
  • U.S. Patent No. 4,451,572 describes a surface modified zeolite produced by reacting the zeolite with an organosilane.
  • WO 99/02264 describes but does not exemplify a supported ultrafine gold particle catalyst that has been rendered hydrophobic for the synthesis of hydrogen peroxide, one method of which is by treatment with silane.
  • U.S. Patent No. 5,028,575 describes a method of removing the surface hydroxyl groups from a Rh/Al 2 O 3 catalyst by silation.
  • SUMMARY OF THE INVENTION Disclosed herein is an improved process for decomposing a hydroperoxide to form a decomposition reaction mixture containing a corresponding alcohol and ketone, the improvement comprising decomposing the hydroperoxide by contacting the hydroperoxide with a catalytic amount of a heterogeneous gold catalyst wherein the gold catalyst has been silanized with an organosilicon reagent. Further disclosed is the process wherein the heterogenous catalyst is supported on a catalyst support member.
  • the present invention provides an improved process for conducting a hydroperoxide decomposition step in an industrial process in which an alkyl or aromatic compound is oxidized to form a mixture of the corresponding alcohol and ketone.
  • cyclohexane can be oxidized to form a mixture containing cyclohexanol (A) and cyclohexanone (K).
  • the industrial process involves two steps: first, cyclohexane is oxidized, forming a reaction mixture containing CHHP; second, CHHP is decomposed, forming a mixture containing K and A.
  • heterogeneous catalytic process relative to processes employing homogenous metal catalysts, such as metal salts or metal/ligand mixtures, include longer catalyst life, improved yields of useful products, and the absence of soluble metal compounds.
  • heterogeneous catalysts subject the process to fouling by water and organic impurities from the oxidation reaction, especially acidic impurities. Removal of these impurities prevents fouling of the catalyst, which thereby extends the catalyst lifetime.
  • the heterogeneous catalysts of the invention comprise Au and Au compounds, preferably applied to suitable solid supports, that have been silanized by an organosilicon reagent.
  • the catalysts after treatment are extremely hydrophobic while showing no decrease in activity as compared to the untreated catalyst.
  • the inventive process may also be performed using Au in the presence of other metals, preferably metals of Periodic Group V ⁇ i, more preferably Pd.
  • the metal to support percentage can vary from about 0.01 to about 50 percent by weight, and is preferably about 0.1 to about 10 wt. percent.
  • Suitable and presently preferred supports include Si ⁇ 2 (silica), AI 2 O 3 (alumina), C (carbon), Ti ⁇ 2 (titania), MgO (magnesia) or ZrO 2 (zirconia).
  • Alumina is a particularly preferred support, and Au supported on alumina is a particularly preferred catalyst of the invention.
  • a preferred catalyst is 0.1-10% Au/0.05-2%Pd on ⁇ -alumina, more preferably 1 %Au/0.1 % Pd on ⁇ -alumina.
  • heterogeneous catalysts of the invention can be obtained already prepared from manufacturers, or they can be prepared from suitable starting materials using methods known in the art.
  • Supported gold catalysts can be prepared by any standard procedure known to give well-dispersed gold, such as sol-gel techniques, evaporative techniques or coatings from colloidal dispersions. In particular, ultra-fine particle sized gold is preferred.
  • Such small particulate gold (often smaller than 10 nm) can be prepared according to Haruta, M., "Size-and Support-Dependency in the Catalysis of Gold", Catalysis Today 36 (1997) 153-166 and Tsubota et al, Preparation of Catalysts V, pp. 695-704 (1991).
  • Such gold preparations produce samples that are purple-pink in color instead of the typical bronze color associated with gold and result in highly dispersed gold catalysts when placed on a suitable support member.
  • These highly dispersed gold particles typically are from about 3 nm to about 25 nm in diameter.
  • the catalyst solid support including Si ⁇ 2, A-2O3, carbon, MgO, zirconia, or Ti ⁇ 2, can be amorphous or crystalline, or a mixture of amorphous and crystalline forms. Selection of an optimal average particle size for the catalyst supports will depend upon such process parameters as reactor residence time and desired reactor flow rates. Generally, the average particle size selected will vary from about 0.005 mm to about 5 mm.
  • Catalysts having a surface area larger than 10 m 2 /g are preferred since increased surface area of the catalyst has a direct correlation with increased decomposition rates in batch experiments. Supports having much larger surface areas can also be employed, but inherent brittleness of high-surface area catalysts, and attendant problems in maintaining an acceptable particle size distribution, will establish a practical upper limit upon catalyst support surface area.
  • a preferred support is alumina; more preferred is ⁇ -alumina and ⁇ -alumina.
  • Adding air or a mixture of air and inert gases to CHHP decomposition mixtures provides higher conversions of process reactants to K and A, since some cyclohexane is oxidized directly to K and A, in addition to K and A being formed by CHHP decomposition.
  • This ancillary process is known as "cyclohexane participation", and is described in detail in Druliner et al., U.S. Patent
  • metals added to the heterogenous catalysts of the invention are for use as promoters, synergist additives, or co-catalysts are selected from Periodic Group Vm, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt. Most preferred is Pd and Pt.
  • One preferred gas that can be added to the reaction mixture is hydrogen.
  • An advantage of the addition of hydrogen is that the K/A ratio can be varied according to need.
  • the addition of hydrogen can also convert impurities or byproducts of the reactions, such as benzene, to more desirable products.
  • the catalysts can be contacted with CHHP by formulation into a catalyst bed, which is arranged to provide intimate contact between catalysts and reactants.
  • catalysts can be slurried with reaction mixtures using techniques known in the art.
  • the process of the invention is suitable for batch or for continuous CHHP decomposition processes. These processes can be performed under a wide variety of conditions.
  • 'Silanized' is defined herein to refer to treatment of the catalyst with either at least one silane, or a mixture of at least one silane and at least one polysiloxane (collectively referred to herein as organosilicon compounds).
  • Suitable silanes have the formula R x Si(R')4_ x wherein R is a nonhydrolyzable aliphatic, cycloaliphatic or aromatic group having at least 8 to about 20 carbon atoms;
  • silanes useful in carrying out the invention include octyltriethoxysilane, nonyltriefhoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriefhoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane and octadecyltriethoxysilane.
  • polydimethylsiloxane PDMS
  • vinyl phenylmethyl terminated dimethyl siloxanes vinyl phenylmethyl terminated polydimethyl siloxane and the like are suitable polysiloxanes.
  • PDMS is a preferred polysiloxane.
  • Weight content of the silane and polysiloxane is about 0.1 to about 5.0 weight %, preferably from about 0.2 to 3 weight %.
  • the ratio of silane to polysiloxane can be 1 silane:2 polysiloxane up to 2 silane: 1 polysiloxane.
  • silanes and polysiloxanes are commercially available or can be prepared by processes known in the art such as those described in "Organosilicon Compounds", S. Pawlenko, et al., New York (1980).
  • the method of addition is not especially critical and the catalyst may be treated with the silane in a number of ways.
  • the silane addition can be made neat or prehydrolyzed to a dry base, from a slurry, a filtration step, during drying or at a size operation such as a fluid energy mill, e.g., micronizer, or media mill as described in greater detail in Niedenzu, et al, U.S. Patent No. 5,501,732, or post blending after micronizing.
  • the polysiloxane addition can be made in conjunction with the silane or post addition to the silanized support.
  • An alternate embodiment that is contemplated is the use of other members of Periodic Groups TV and V in place of Si, such as Ge, P, and As.
  • the catalysts of the invention would thereby be treated with compounds that are the equivalent of the silanes of the instant invention, such as R x Ge(R') 4 _ x , R X P(R') 3 . X " , etc.
  • the following definitions are used herein and should be referred to for claim interpretation.
  • R-F-CHHP CC response factor for CHHP
  • %CHHP decomposition were determined from calibration solutions containing known amounts of CHHP and CB, and was calculated from the equations:
  • %CHHP decompostion 100 x 1 - (area % CHHP/area % CB) init ⁇ l

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Processus catalytique amélioré pour décomposer l'alkyle ou les hydroperoxydes aromatiques, qui utilise une quantité catalytique d'un catalyseur Au hétérogène qui a été traité avec un réactif organosilicié.
PCT/US2000/022867 2000-08-18 2000-08-18 Catalyseur ameliore de la decomposition de l'hydroperoxyde WO2002016296A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CNB008198322A CN1203041C (zh) 2000-08-18 2000-08-18 改良的氢过氧化物分解催化剂
AU2000267916A AU2000267916A1 (en) 2000-08-18 2000-08-18 Improved hydroperoxide decomposition catalyst
US10/344,443 US6806390B1 (en) 2000-08-18 2000-08-18 Hydroperoxide decomposition catalyst
EP00955769A EP1309534B1 (fr) 2000-08-18 2000-08-18 Catalyseur ameliore de la decomposition de l'hydroperoxyde
DE60023358T DE60023358T2 (de) 2000-08-18 2000-08-18 Verbesserter hydroperoxid zersetzungskatalysator
KR10-2003-7002297A KR20030034145A (ko) 2000-08-18 2000-08-18 개선된 히드로퍼옥사이드 분해반응 촉매
JP2002521172A JP2004506703A (ja) 2000-08-18 2000-08-18 改良されたヒドロペルオキシド分解触媒
PCT/US2000/022867 WO2002016296A1 (fr) 2000-08-18 2000-08-18 Catalyseur ameliore de la decomposition de l'hydroperoxyde

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2000/022867 WO2002016296A1 (fr) 2000-08-18 2000-08-18 Catalyseur ameliore de la decomposition de l'hydroperoxyde

Publications (1)

Publication Number Publication Date
WO2002016296A1 true WO2002016296A1 (fr) 2002-02-28

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PCT/US2000/022867 WO2002016296A1 (fr) 2000-08-18 2000-08-18 Catalyseur ameliore de la decomposition de l'hydroperoxyde

Country Status (8)

Country Link
US (1) US6806390B1 (fr)
EP (1) EP1309534B1 (fr)
JP (1) JP2004506703A (fr)
KR (1) KR20030034145A (fr)
CN (1) CN1203041C (fr)
AU (1) AU2000267916A1 (fr)
DE (1) DE60023358T2 (fr)
WO (1) WO2002016296A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7541500B2 (en) 2006-02-27 2009-06-02 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone

Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
CN1296333C (zh) * 2004-07-13 2007-01-24 中国科学院大连化学物理研究所 一种催化分解环己烷过氧化氢方法
US7081552B2 (en) * 2004-08-17 2006-07-25 Solutia Inc. Catalysts for cycloalkanes oxidation and decomposition of cycloalkyl hydroperoxide
US7709685B2 (en) * 2007-03-16 2010-05-04 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
JP2009035519A (ja) 2007-08-03 2009-02-19 Sumitomo Chemical Co Ltd シクロアルカノール及び／又はシクロアルカノンの製造方法
JP2009227653A (ja) * 2008-02-29 2009-10-08 Sumitomo Chemical Co Ltd シクロアルカノール及び／又はシクロアルカノンの製造方法
CN102407118B (zh) * 2010-09-21 2013-06-05 中国石油化工股份有限公司 不饱和烃加氢的催化剂及其应用
CN102408290B (zh) * 2010-09-21 2014-05-28 中国石油化工股份有限公司 不饱和烃加氢饱和为烷烃的方法
EP2845642A1 (fr) * 2013-09-09 2015-03-11 Airbus Defence and Space Limited Catalyseur de peroxyde d'hydrogène
CN108654684B (zh) * 2017-03-29 2020-09-04 中国科学院大连化学物理研究所 一种b/l酸修饰的有机硅球催化剂及制备和其应用

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EP0653401A1 (fr) * 1993-11-12 1995-05-17 Texaco Development Corporation Utilisation de catalyseurs de palladium supportés dans la préparation de l'alcool tertiobutylique de l'hydropéroxide tertiobutylique
WO1998034894A2 (fr) * 1997-02-11 1998-08-13 E.I. Du Pont De Nemours And Company Procede de decomposition d'hydroperoxydes

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NL7802125A (nl) * 1978-02-25 1979-08-28 Stamicarbon Werkwijze voor het bereiden van cycloalkanolen en cycloalkanonen.
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US5149881A (en) * 1990-05-21 1992-09-22 Mitsubishi Kasei Corporation Method for producing methyl isobutyl ketone
EP0653401A1 (fr) * 1993-11-12 1995-05-17 Texaco Development Corporation Utilisation de catalyseurs de palladium supportés dans la préparation de l'alcool tertiobutylique de l'hydropéroxide tertiobutylique
WO1998034894A2 (fr) * 1997-02-11 1998-08-13 E.I. Du Pont De Nemours And Company Procede de decomposition d'hydroperoxydes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7541500B2 (en) 2006-02-27 2009-06-02 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone

Also Published As

Publication number Publication date
DE60023358D1 (de) 2006-03-02
EP1309534A1 (fr) 2003-05-14
CN1454199A (zh) 2003-11-05
KR20030034145A (ko) 2003-05-01
US6806390B1 (en) 2004-10-19
AU2000267916A1 (en) 2002-03-04
EP1309534B1 (fr) 2005-10-19
JP2004506703A (ja) 2004-03-04
CN1203041C (zh) 2005-05-25
DE60023358T2 (de) 2006-07-13

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